The catalyzed reaction of alkanols with ammonia or amines to produce a mixture of alkylamines is known. Various catalysts are also known for use in the amination process. For example, cobalt, nickel, copper, and palladium, have been used in the reductive amination of alcohols; and, silica-alumina and zeolite-type catalysts have been used in the direct amination of alcohols.
Production of a non-equilibrium distribution of products from the amination process is often desired and has been achieved by altering reaction conditions and/or catalyst systems. Examples of catalyst systems used to produce a non-equilibrium split of alkyl amines are described below:
U.S. Pat. No. 3,384,667 (Hamilton, 1968) discloses a method of producing primary and secondary amines in preference to tertiary amines by reacting an alcohol with ammonia in the presence of a dehydrated crystalline metal aluminosilicate catalyst having a pore size of 5 to about 10 .ANG.. The original metal in the aluminosilicate catalyst can be replaced by a variety of cations, such as barium, calcium, and magnesium. Appropriate reaction temperatures were reported to be 200 to 300.degree. C.
U.S. Pat. No. 4,082,805 (Kaeding, 1978) discloses a process for producing primary aliphatic amines over secondary or tertiary amines by reacting a C.sub.1 -C.sub.5 alcohol or ether with ammonia in the presence of an aluminosilicate catalyst having a high silica to alumina ratio; i.e., greater than 5 and preferably greater than 30. Operative catalysts include ZSM-5, ZSM-11 or ZSM-21. Reaction temperatures are 300 to 500.degree. C.
U.S. Pat. No. 4,254,061 (Weigert, 1981) discloses a catalytic process for making monomethylamine in which methanol and ammonia, in amounts so as to provide a carbon/nitrogen ratio of 0.5 to 1.5, are reacted over a dehydrated crystalline aluminosilicate catalyst selected from:
mordenite wherein the primary cation is Li, Na, K. Ca, Sr, Ba, Ce, Zn, or Cr; PA1 ferrierite wherein the primary metal cation is Li, Na, K. Ca, Sr, Ba, Ce, or Fe; PA1 erionite ore; PA1 calcium erionite; and PA1 clinoptilolite ore. PA1 Predominantly primary and secondary amines and little or no tertiary amines can be produced at moderate temperatures and pressures; PA1 Predominantly primary amines can be produced with branched alcohols such as isopropanol; PA1 High conversion rates are achieved with a relatively small amount of cobalt or nickel in the catalyst; and PA1 There is little or no deactivation of catalyst over several reaction runs.
The reaction temperature is 250 to 475.degree. C. at pressures of 1-1000 psi.
U.S. Pat. No. 4,398,041 (Cochran et al., 1983) discloses a two-stage process for converting C.sub.1 -C.sub.4 alcohol to a non-equilibrium controlled distribution of primary, secondary, and tertiary amines. Shape selective crystalline aluminosilicate zeolite catalysts are used in the process which is conducted at temperatures between about 250 to 425.degree. C.
U.S. Pat. No. 4,918,234 (Deeba, 1990) discloses an improved process for producing C.sub.2 to C.sub.4 alkylamines by the reaction of a C.sub.2 to C.sub.4 alkanol with ammonia in the presence of hydrogen and a crystalline aluminosilicate catalyst at temperatures of 170 to 220.degree. C., to produce non-equilibrium split of alkylamines. The crystalline aluminosilicate zeolite catalyst system is a Y zeolite containing predominantly cobalt or nickel ions.